CN105111040B - A kind of vinylidene is Material synthesis tetrafluoropropene HFO1234yf method - Google Patents
A kind of vinylidene is Material synthesis tetrafluoropropene HFO1234yf method Download PDFInfo
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- CN105111040B CN105111040B CN201510508048.8A CN201510508048A CN105111040B CN 105111040 B CN105111040 B CN 105111040B CN 201510508048 A CN201510508048 A CN 201510508048A CN 105111040 B CN105111040 B CN 105111040B
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- vinylidene
- trifluoroacetic acid
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Abstract
The invention discloses a kind of method that vinylidene is Material synthesis tetrafluoropropene HFO1234yf, preparation process includes：(a) pretreatment of catalyst；(b) synthetic reaction：Trifluoroacetic acid enters in reactor, and the catalyst prepared in above-mentioned steps is added in the reactor, is passed through vinylidene fluoride monomers, 300 600 DEG C of reaction temperature, reaction pressure is 1~5Mpa, by the mol ratio 18 of trifluoroacetic acid and vinylidene:1, catalyst dosage is the 10 50% of trifluoroacetic acid quality, and product enters cooling separator with gaseous state, and gas obtains product through alkaline solution adsorption refining.The trifluoroacetic acid that the present invention is easily bought using in the market with vinylidene as raw material, raw material route find more be easy to get, it is simple in construction, HFO 1234yf production scale is not restricted, it is to avoid general raw material output is small, is difficult the shortcoming of buying.
Description
Technical field
The present invention relates to a kind of tetrafluoropropene preparation method, and in particular to a kind of vinylidene is Material synthesis tetrafluoropropene
HFO1234yf method.
Background technology
HFO-1234yf, molecular formula is CF3CF=CH2, -28.3 DEG C of boiling point, No. CAS：754-12-1, its ODP are 0, GWP
For 4, with good lifetime climate performance (LCCP)；Belong to hypotoxicity, and toxicity is less than HFC-134a；Weak combustibility is stable
Property and compatibility preferably, material sealing is good, is novel environment friendly with the refrigeration performance parameter with HFC-134a closely
Refrigerant.HFO-1234yf can also be applied to extinguishing chemical, heat transfer medium, propellant, foaming agent, foaming agent, gas medium, go out
Microbial inoculum carrier, polymer monomer, remove granule fluid, carrier gas flow, grinding with polishing agent, replace drier, electricity circulation workflow
The fields such as body.
Blake P.G., Pritchard H are in document " The thermal decomposition of
In trifluoroacetic acid [J] .J.Chem.Soc. (B) ", trifluoroacetic acid is have studied in 573-663K temperature ranges
Thermal degradation mechanism, thus it is speculated that going out the reaction mechanism of trifluoroacetic acid is：
CF3COOH→HF+·CF2COO·
CF2COO→:CF2+CO2
US20060842585 is that HFC-1225ve generates HFC- with hydrogen addition reaction in the presence of a hydrogenation catalyst
245cb, then HFC-245cb gas phase dehydrofluorinations produce HFO-1234yf, the key technology of this route is the choosing of catalyst
Select and prepare.
US2006084244 is that in the presence of a hydrogenation catalyst, HFC-1225ye generates HFC-245cb with hydrogen addition, connects
HFC-245cb and produce HFO-1234yf with alkaline aqueous solution reaction in the presence of phase transfer catalyst and non-aqueous, Non-alchoholic solvents.
Using HFC-245cb, the dehydrofluorination in the presence of Dehydrofluorination catalyst is generated US20060816650 public technologies
HFO-1234yf and HFO-1234ze, Dehydrofluorination catalyst choice fluorided alumina and/or aluminum fluoride.And propose simultaneously with anti-
Answer product to be separated with the mode of HF formation azeotropic mixtures and carry HFO-1234yfHFO-1234Ze.
Raw material sources of the prior art are restricted, and the production scale for constraining HFO-1234yf is more easy to, it is necessary to find
, raw material route simple in construction is improved.
The content of the invention
It is raw material present invention aims at above-mentioned technical problem present in prior art is solved there is provided a kind of vinylidene
The method for synthesizing tetrafluoropropene HFO1234yf, it is to avoid general raw material output is small, is difficult the shortcoming of buying.
In order to solve the above-mentioned technical problem, the present invention is adopted the following technical scheme that：
A kind of vinylidene is Material synthesis tetrafluoropropene HFO1234yf method, it is characterised in that preparation process includes：
(a) pretreatment of catalyst：
By γ-Al2O3, account for γ-Al2O3Mass percent is 5~15% (wt) ammonium fluoride (NH4F), γ-Al are accounted for2O3Matter
The water that percentage is 100~500% (wt) is measured, γ-Al are accounted for2O3Mass percent is 1~5% (wt) boron trifluoride ether solution,
Account for γ-Al2O3Quality 0.2%-2% LaN03, it is added in reactor, soaks 10-40h, centrifugation, by solid in 80-150 DEG C
Dry after 15-40h, catalyst is made after 400-800 DEG C, roasting 3-6h are gradually heating in atmosphere；
(b) synthetic reaction：
Trifluoroacetic acid enters in reactor, and the catalyst prepared in above-mentioned steps is added in the reactor, inclined fluorine second is passed through
Alkene monomer, 300-600 DEG C of reaction temperature, reaction pressure is 1~5Mpa, by trifluoroacetic acid and the mol ratio 1-8 of vinylidene:1,
Catalyst dosage is the 10-50% of trifluoroacetic acid quality, and product enters cooling separator with gaseous state, and gas is through alkaline solution
Adsorption refining, obtains product.
The present invention is by adopting the above-described technical solution, have the advantages that：
Lanthanum nitrate, γ-Al used in the present invention2O3, BFEE, ammonium fluoride be commercially available prod, Er Qieben
The trifluoroacetic acid that invention is easily bought using in the market is with vinylidene as raw material, and raw material route searching is more easy to get, structure letter
Single, HFO-1234yf production scale is easily extended, it is to avoid general raw material output is small, is difficult the shortcoming of buying.
Embodiment
The present invention uses trifluoroacetic acid and vinylidene reaction synthesis tetrafluoropropene HFO1234yF, reaction scheme is illustrated such as
Under：
CF3COOH→HF+·CF2COO· (1)
CF2COO→:CF2+CO2 (2)
A kind of vinylidene of the present invention is Material synthesis tetrafluoropropene HFO1234yf method, passes through following step
It is rapid to prepare：
(a) pretreatment of catalyst：
By γ-Al2O3, account for γ-Al2O3Mass percent is 5~15% (wt) ammonium fluoride (NH4F), γ-Al are accounted for2O3Matter
The water that percentage is 100~500% (wt) is measured, γ-Al are accounted for2O3Mass percent is 1~5% (wt) boron trifluoride ether solution,
Account for γ-Al2O3Quality 0.2%-2% LaN03, it is added in reactor, soaks 10-40h, centrifugation, by solid in 80-150 DEG C
Dry after 15-40h, catalyst is made after 400-800 DEG C, roasting 3-6h are gradually heating in atmosphere.Used in the step
Lanthanum nitrate, γ-Al2O3, BFEE, ammonium fluoride be commercially available prod.
(b) synthetic reaction：
Trifluoroacetic acid enters in reactor, and the catalyst prepared in above-mentioned steps is added in the reactor, inclined fluorine second is passed through
Alkene monomer, 300-600 DEG C of reaction temperature, reaction pressure is 1~5Mpa, by trifluoroacetic acid and the mol ratio 1-8 of vinylidene:1,
Catalyst dosage is the 10-50% of trifluoroacetic acid quality, and product enters cooling separator with gaseous state, and gas is through alkaline solution
Adsorption refining, the alkaline solution is mainly used in absorbing carbon dioxide, hydrogen fluoride etc., does not limit herein, such as potassium hydroxide, hydrogen-oxygen
Change sodium etc., finally prepare tetrafluoropropene HFO1234yf.The trifluoroacetic acid easily bought using in the market in the step with partially
PVF is used as raw material.
Embodiment 1：
(a) pretreatment of catalyst：
By 100Kg γ-Al2O3, 10Kg NH4F, 300Kg water, 2Kg boron trifluoride ether solutions, 1Kg LaN03, plus
Enter into 1000L reactors, soak 24h, centrifugation, by solid in after 120 DEG C of dry 30h, is gradually heating to 600 in atmosphere
DEG C, catalyst is made after roasting 4h.
(b) synthetic reaction：
100Kg trifluoroacetic acids enter in 500L reactors, and pyrolytic reaction is carried out at a temperature of 400 DEG C, add in the reactor
Enter the catalyst prepared in 30Kg steps 1, be passed through vinylidene fluoride monomers and continue to react, 600 DEG C of reaction temperature.Reaction pressure is
3Mpa, by the mol ratio 4 of trifluoroacetic acid and vinylidene:1, product enters cooling separator with gaseous state, and gas is through alkalescence
Solution adsorption refining, obtains product, and numbering is M-1.
Embodiment 2：
(a) pretreatment of catalyst：
By 100Kg γ-Al2O3, 5Kg NH4F, 100Kg water, 1Kg boron trifluoride ether solutions, 0.2Kg LaN03,
It is added in 500L reactors, soaks 10h, centrifugation, by solid in after 80 DEG C of dry 40h, is gradually heating to 400 in atmosphere
DEG C, catalyst is made after roasting 6h.
(b) synthetic reaction：
100Kg trifluoroacetic acids enter in 500L reactors, and pyrolytic reaction is carried out at a temperature of 300 DEG C, add in the reactor
Enter the catalyst prepared in 10Kg steps 1, be passed through vinylidene fluoride monomers and continue to react, 500 DEG C of reaction temperature.Reaction pressure is
1Mpa, by the mol ratio 1 of trifluoroacetic acid and vinylidene:1, product enters cooling separator with gaseous state, and gas is through alkalescence
Solution adsorption refining, obtains product, and numbering is M-2.
Embodiment 3：
(a) pretreatment of catalyst：
By 100Kg γ-Al2O3, 15Kg NH4F, 500Kg water, 1Kg boron trifluoride ether solutions, 2Kg LaN03, plus
Enter into 500L reactors, soak 40h, centrifugation, by solid in after 150 DEG C of dry 15h, is gradually heating to 800 DEG C in atmosphere,
It is calcined after 3h and catalyst is made.
(b) synthetic reaction：
100Kg trifluoroacetic acids enter in 500L reactors, and pyrolytic reaction is carried out at a temperature of 600 DEG C, add in the reactor
Enter the catalyst prepared in 50Kg steps 1, be passed through vinylidene fluoride monomers and continue to react, 1000 DEG C of reaction temperature.Reaction pressure is
5Mpa, by the mol ratio 8 of trifluoroacetic acid and vinylidene:1, product enters cooling separator with gaseous state, and gas is through alkalescence
Solution adsorption refining, obtains product, and numbering is M-3.
Comparative example 1：
Ammonium fluoride is added without, the other the same as in Example 1.Products obtained therefrom numbering is M-4.
Comparative example 2：
LaN03It is added without, the other the same as in Example 1.Products obtained therefrom numbering is M-5.
Comparative example 3：
Boron trifluoride ether solution is added without, the other the same as in Example 1.Products obtained therefrom numbering is M-6.
Comparative example 4：
Catalyst is added without, the other the same as in Example 1.Products obtained therefrom numbering is M-7.
Product M-1~M-3 and comparative example M-4~M-7 that the embodiment of the present invention is obtained, are calculated as follows reaction tetrafluoro third
Alkene HFO1234yf yields, it is as a result as shown in table 1 below：
| Numbering | Tetrafluoropropene HFO1234yf yields/% |
| M-1 | 22 |
| M-2 | 19 |
| M-3 | 27 |
| M-4 | 15 |
| M-5 | 14 |
| M-6 | 15 |
| M-7 | 10 |
The comparison for the test specimen tetrafluoropropene HFO1234yf yields that the different process of table 1 is made
Lanthanum nitrate, γ-Al used in the present invention2O3, BFEE, ammonium fluoride be commercially available prod, Er Qieben
The trifluoroacetic acid that invention is easily bought using in the market is with vinylidene as raw material, and raw material route searching is more easy to get, structure letter
Single, HFO-1234yf production scale is easily extended, it is to avoid general raw material output is small, is difficult the shortcoming of buying.
The specific embodiment of the present invention is these are only, but the technical characteristic of the present invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technique effect is realized, made simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (1)
1. a kind of vinylidene is Material synthesis tetrafluoropropene HFO1234yf method, it is characterised in that preparation process includes：
(a) pretreatment of catalyst：
By γ-Al2O3, account for γ-Al2O3Mass percent is 5~15% (wt) ammonium fluoride (NH4F), γ-Al are accounted for2O3Quality hundred
Divide than the water for 100~500% (wt), account for γ-Al2O3Mass percent is 1~5% (wt) boron trifluoride ether solution, is accounted for
γ-Al2O3Quality 0.2%-2% LaNO3, it is added in reactor, soaks 10-40h, centrifugation is dry in 80-150 DEG C by solid
After dry 15-40h, catalyst is made after 400-800 DEG C, roasting 3-6h are gradually heating in atmosphere；
(b) synthetic reaction：
Trifluoroacetic acid enters in reactor, and the catalyst prepared in above-mentioned steps is added in the reactor, vinylidene list is passed through
Body, 300-600 DEG C of reaction temperature, reaction pressure is 1~5Mpa, by trifluoroacetic acid and the mol ratio 1-8 of vinylidene:1, catalysis
Agent dosage is the 10-50% of trifluoroacetic acid quality, and product enters cooling separator with gaseous state, and gas is adsorbed through alkaline solution
It is refined, obtain product.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626130A (en) * | 2012-08-27 | 2014-03-12 | 切弗朗菲利浦化学公司 | Vapor phase preparation of fluorided solid oxides |
| CN104169246A (en) * | 2012-03-14 | 2014-11-26 | 旭硝子株式会社 | Production method for 2,3,3,3-tetra-fluoropropene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013227244A (en) * | 2012-04-25 | 2013-11-07 | Asahi Glass Co Ltd | Method for producing 2,3,3,3-tetrafluoropropene |
| JP2015110533A (en) * | 2013-12-06 | 2015-06-18 | 旭硝子株式会社 | Method of producing 2,3,3,3-tetrafluoropropene and 1,1-difluoroethylene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104169246A (en) * | 2012-03-14 | 2014-11-26 | 旭硝子株式会社 | Production method for 2,3,3,3-tetra-fluoropropene |
| CN103626130A (en) * | 2012-08-27 | 2014-03-12 | 切弗朗菲利浦化学公司 | Vapor phase preparation of fluorided solid oxides |
Non-Patent Citations (2)
| Title |
|---|
| P. G. Blake.The Thermal Decomposition of Trifluoroacetic acid.《J. Chem. Soc. (B)》.1967,282-286. * |
| T. J. Wallington et al..Atmospheric chemistry of short-chain haloolefins: Photochemical ozone creation potentials (POCPs), global warming potentials (GWPs), and ozone depletion potentials (ODPs).《Chemosphere》.2014,第129卷135-141. * |
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